Process for dyeing fibre materials of polyacrylonitrile of acrylonitrile-containing copolymers

ABSTRACT

Process for dyeing textile fiber materials of polyacrylonitrile or copolymers of acrylonitrile with cationic dyestuffs which comprises carrying out the dyeing in the presence of amidinium compounds of the formula   WHEREIN R1, R2, R3, R4 and R5 are, independently of one another, hydrogen, an optionally substituted alkyl, cycloakyl, aralkyl or aryl group; R2 may form with R1 or R3 and/or R4 with R5 a heterocyclic ring, and X is an anion.

United States Patent Walz et a1.

Feb. 8, 1972 [54] PROCESS FOR DYEING FIBRE MATERIALS 0F POLYACRYLONITRILE OF ACRYLONITRILE-CONTAINING COPOLYMERS [72] Inventors: Klaus Wall, Leverkusen-Wiesdorf; Walter l-lees, Koeln-Hoehenhaus; Mathieu Quaedvlieg, Opladen, all of Germany [73] Assignee: Farbenfabriken Bayer Aktiengesellschaft,

Leverkusen, Germany [22] Filed: Jan. 28, 1969 [21] App1.No.: 794,804

[30] Foreign Application Priority Data Feb. 9, 1968 Germany ..F 54782 [52] US. Cl ..8/172, 8/177 AB [51] Int. Cl. ..D06p 3/70 [58] FieldofSearch ..8/84, 172, 177 AB [56] References Cited UNITED STATES PATENTS 3,529,920 9/1970 Walz et a1 ..8/177 AB 2,183,754 12/1939 Schlack 8/17? X 2,607,803 8/1952 Lecher et al. ..8/84 X FOREIGN PATENTS OR APPLICATIONS 634,304 12/1963 Belgium.... ..8/172 1,205,528 11/1965 Germany ..8/84

Primary ExaminerGeorge F. Lesmes Assistant Examiner-T. J. Herbert, Jr. AttorneyPlumley, Tyner & Sandt ABSTRACT Were R], R R R and R are, independently of one another, hydrogen, an optionally substituted a1ky1, cycloakyl, aralkyl or aryl group; R may form with R or R; and/0r R with R, a heterocyclic ring, and X is an anion.

2 Claims, No Drawings PROCESS FOR DYEING FIBRE MATERIALS OF POLYACRYLONITRILE OF ACRYLONITRILE- CONTAINING COPOLYMERS The present invention relates to a process for dyeing fiber in which R,, R R R and R stand, independently of one another, for hydrogen, for an optionally substituted alkyl,

cycloalkyl, aralkyl or aryl group; R may form with R, or R and/or R with R a heterocyclic ring, and X is an anion.

Alkyl groups are particularly those which contain one to 12 carbon atoms, for example, the methyl, ethyl, propyl,

isopropyl, butyl, hexyl, octyl, decyl and the dodecyl group;

aralkyl groups are particularly the benzyland phenylethyl radical; aryl groups are particularly the phenyl and naphthyl radical.

As substitutents for the alkyl groups there may be mentioned in particular the hydroxyl group, the phenoxy, chlorophenoxy and dichloro-phenoxy radical; for the cycloalkyl, aralkyl and aryl radicals primarily lower alkyl groups, e. g., the methyl and ethyl group, as well as halogen atoms, e.g., the chloro or bromo atom, may be used.

As anion X there may be mention, in particular, Cl, Br, S0 N0 HCOO'. CH COO, (II-i 80; and

eta-Q-sm:

The compounds to be used according to the invention can be produced by various known methods, for example, by reacting imino ether hydrochlorides with ammonia or amines, or by reacting said amide-acid chloride or acid amide-dialkyl sulphate complexes with ammonia or amines lcf. Houben- Weyl Methoden der organischen Chemie," vol. VIII (1952) pages 702 et seq., as well as German Published Pat. No. 1,205,528].

Examples of the amidinium compounds to be used for the cycloalkyl groups are particularly the cyclohexyl, process according to the invention are the compounds of the tetrahydronaphthalene and decahydronapht halerie radical; formula l i n which R R and X have the following meaning R1 R2 a R4 R5 X H CHa- CH3 nCaHanC Hn- CHzOSOr om- CH H 011,050,- H.-. CH:--- CH3- H nCmHz CHaOSOr H-.- CH3 CH3 H nC12Hz5 CHzOSOr H... CH3- CH3- H CHaOSOr H CH3- CH3 OHr- C1 H CH on? H g 010- 01- 11... CHr- CHa-- H 011?- 01- H. cm- 0113- H @omom- 01- H.... CH3-- CH H @OCHzCHz- CHzOSOa" a R4 R5 X CzHr- H I'ICQHH- CHgOSOr CzHr- H BClHq- OH OSOr CzHr- H nCsHn- CHQOSOQ H H CHaOSOa H H HC4H9- cm-Qsor H 02m CzH5-- H @0112- 0113050 CH3- CH3 CH: I1C4HnnCrHw 01130303" CH;; 0H,- CH H @0112- 01130803- ca 0H,- 011,- H CHaOSOa' R1 R2 R3 R4 R5 X CH3- CzHr- H H H C1 H 0113- H HOCHzCHr HooH2oH2 cmosor nC H CH om- H CHzOSOs IIC3H7- CH3- CH3- C2H5- HO CHCHz CHaOSOa Q- H H H H CH C o o G H H CH CH o1- Q-GHT- H H OH; OH Br- Q-CHZ- 025,- H CgH5- H 01- Q-QHT- IIC4HI' H H H 01- nC H H H 0 H3 0 Ha N03 Further suitable compounds of the formula (I) are the following, for example:

1 i' i (CH2)sCNHC4Hn CHaO S 0 (CHz)5C- H CHgO S O;-

IfIH H2)s-CN 6 Q11 0 S 03" N(C2H5)2 3)2 CH3C\ OHgO S 03" C H C\ C1- 16 N b L,

a)2 v a)z y HC\ CHaOSOs" HC\ S0 N H N b N(C2H5)2 N(C2H5) HC\ 01130803" HC\ CHaOSOa N S N S 02 Cationic dyestuffs which may be used are dyestuffs of very diverse compound classes, for example, diphenylmethane, triphenylmethane and rhodamine dyestuffs, omnium groupcontaining azo and anthraquinone dyestuffs, furthermore thiazine, oxazine, methine and azomethine dyestuffs as are described, for example, in American Dyestuff Reporter (1954), pages 432-433, in the US. Pat. No. 2,716,655 and in the British Pat. Nos. 785,988, 871,624, 791,932, 930,471.

The necessary quantities of the amidinium compounds of the formula (I) to be used according to the invention can readily be determined by preliminary experiments. In general, these compounds are used in amounts of about 1.5-3 percent, referred to the weight of the dyeing material used. 7

Suitable acrylonitrile-containing copolymers are, for example, those containing vinyl chloride, vinylidene chloride, vinyl. acetate, vinyl chloroacetate, vinyl 7 alcohol, acrylic and methacrylic acid, acrylic and methacrylic acid esters, allylchloroacetate, or basic vinyl compounds, such as vinyl imidazole, vinyl benzimidazole, vinyl pyridine, vinyl methyl pyridine, vinyl pyrimidine, provided the proportion of these comonomers in the copolymer does not exceed 20 percent by weight. g

The dyeing of the polyacrylonitrile fiber materials can be carried out in conventional manner by introducing the material to be dyed into an aqueous bath heated to about 5060 C. and containing the cationic dyestuff, amidinium compounds of the formula (I), additives of salts, such as sodium acetate or sodium sulphate, furthermore acids, such as acetic acid or formic acid, subsequently raising the temperature of the dyebath to approximately C. in the course of about 30 minutes and then keeping the dyebath at this temperature until the bath is exhausted. Alternatively, it is also possible to add subsequently the cationic dyestuff to the dyebath, for example, when the temperature of the bath has risen to about 60 C. It is also possible to pretreat the dyeing material at a temperature of about 40-100 C. with a liquor which contains the customary salts and acids as well as the amidinium compounds of 5 the formula (1), but no dyestuff, then to add the dyestuff and to carry out the dyeing process at 100 C. Finally, it is also possible to introduce the dyeing material immediately into the dyebath heated to approximately 100 C. and containing the amidinium compounds of the formula (I). The amidinium compounds can also be used in combination with basic compounds, as have previously been used as levelling auxiliary agents for the dyeing of polyacrylonitrile fibers, for example, with quaternary ammonium salts containing higher alkyl radicals, such as cetylbenzyl-dimethyl-ammonium chloride.

With the aid of the process according to the invention it is possible to dye fiber materials of the greatest variety consisting of polyacrylonitrile or acrylonitrile-containing copolymers or containing polymers or copolymers of this type, for example, spun-sheathed cables, combed materials, flocks, yarns, woven or knitted fabrics, with outstanding levelness and in deep shades.

The amidinium compounds to be used according to the invention improve the migration of the cationic dyestuffs in the fiber, even without the concurrent use of electrolytes, such as sodium sulphate, without reducing affinity of the fibers for the cationic dyestuffs in a degree worth mentioning.

EXAMPLE 1 Yarns of polyacrylonitrile fibers are introduced, in a goodsto-liquor ratio 1:40, into a bath heated to 80 C. and containing, per litre, 0.2 g. of the dyestuff obtained by quaternising 1- methylamino-4-(3'-dimethylamino-propylamino)-anthraquinone with dimethyl sulphate, 0.25 g. sodium acetate, 0.3 g. glacial acetic acid and 0.6 g. of the compound of the formula HO CHaOSOa" The bath is then heated to 98 C. and kept at this temperature for 60 minutes. A blue dyeing of excellent levelness is obtained.

Instead of the N-butyl-N'-cyc1ohexy1-formamidiniummethosulphate used, the same good result was obtained with the use of one of the following amidinium compounds:

CHQOS O:-

NH H

EXAMPLE 2 a)2 HG CHQOS Or The bath is heated to 98 C. and kept at this temperature for 60 minutes. A level blue dyeing is obtained.

A blue dyeing of the same levelness was obtained by using, instead of the amidinium compound used above, the same amount of one of the following amidinium compounds:

HC c1130 s03- CH OSOT EXAMPLE 3 The bath is then heated to 98 C. and kept at this temperature for 60 minutes. A greenish blue dyeing of excellent levelness is obtained.

We claim:

1. Process for the dyeing of fiber materials produced from polyacrylonitrile or acrylonitrile-containing copolymers with cationic dyestuffs, characterized by carrying out the dyeing process in the presence of amidinium compounds of the formula in which R,, R R R and R stand, independently of one another, for hydrogen, for an optionally substituted alkyl, cycloakyl, aralkyl or aryl group; R may form with R, or R and/or R, with R a heterocyclic ring, and X is an anion.

2. Fiber materials of polyacrylonitrile or acrylonitrile-containing copolymers dyed according to claim 1.

g a 3k 

2. Fiber materials of polyacrylonitrile or acrylonitrile-containing copolymers dyed according to claim
 1. 